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In Situ Enzyme Immobilization with Oxygen-Sensitive Luminescent Metal-Organic Frameworks to Realize "All-in-One" Multifunctions.

Metal-organic frameworks (MOFs) for enzyme immobilization have already shown superior tunable and designable characteristics, however, their devisable responsive properties have rarely been exploited. Herein, we integrated a responsive MOF into MOF-enzyme composite to propose an "all-in-one" multifunctional composite with catalytic and luminescence functions implemented within a single particle. As a proof-of-concept, glucose oxidase (GOx) was in situ encapsulated within an oxygen (O₂)-sensitive, noble-metal-free luminescent Cu(I) triazolate framework (MAF-2), namely GOx@MAF-2. Owing to the rigid scaffold of MAF-2 and confinement effect, the GOx@MAF-2 composite showed significantly improved stability (shelf life to 60 days and heat-resistance up to 80 ⁰C) with good selectivity and recyclability. More importantly, the integration of the O₂-sensitivity of MAF-2 allowed the GOx@MAF-2 composite rapidly and reversibly response toward dissolved O₂, which realized direct and ratiometric sensing of glucose without the needs of chromogenic substrates, cascade enzymatic reactions or electrode system. A high sensitivity with a detection limit of 1.4 µM glucose was achieved, and the glucose in human sera was accurately determined. The strategy opens a new application of MOFs and can be facilely extended to various MOF-enzyme composites due to the multifunctionality of MOFs.

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